New 1:4-dihydroxy-5-acylaminoanthraquinones



3,005,822 NEW 1:4-DIHYDROXY-5-ACYLAMINOANTHRA- QUINONES This invention provides as new dyestuffs 1:4-dihydroxy- S-acylaminoanthraquinones of which the acyl radical is the radical of a monocarboxylic acid.

The invention also provides a process for the manufacture of the aforesaid dyestuffs, wherein a 1:4-dihydroxy- S-aminoanthraquinone is acylated with a reactive derivative of a monocarboxylic acid.

As acylating agents there are advantageously used halides of monocarboxylic acids of low molecular weight, for example, of aliphatic monocarboxylic acids containing 2-12, and advantageously 4-12 carbon atoms, for example, the halides of acetic acid, propionic acid, butyric acid, isobutyric acid, caproic acid or lauric acid. Of special interest are the halides of aromatic monocarboxylic acids of the benzene series, especially benzoic acid and substitution products of benzoic acid, for example, salicylic acid, para-hydroxybenzoic acid or paraor metamethoxybenzoic acid, or alkyl-substituted benzoic acid, such as ortho-, metaor para-toluylic acid and halogensubstituted benzoic acids, such as ortho-chloroor orthobromobenzoic acid. There may also be mentioned the halides of alicyclic carboxylic acids, for example, cyclohexane carboxylic acid, and heterocyclic acids, for example, furane 2-carboxylic acid or pyridine-3-carboxylic acid.

As halides there are advantageously used the chlorides of the aforesaid acids.

The acylation may be carried out by a method in itself known, for example, in an inert organic solvent, such as nitrobenzene or chlorobenzene, advantageously, in the presence of an acid-binding agent, for example, a tertiary base such as pyridine or dimethyl aniline, and advantageously at a raised temperature.

The 1:4-dihydroxy-S-acylaminoanthraquinones of this invention are excellently suited, especially after a suitable pasting operation which may be coupled with a reprecipitation, for example, from sulfuric acid, for dyeing or printing structures of hydrophobic material, especially fibers of polyesters, for example, polyethylene terephthalate, Which fibers are known under the name Terylene or Dacron. Strong pure orange-red dyeings, which are distinguished more especially by their good fastness to light and sublimation, are obtained by the usual dyeing methods, for example, with a dye liquor which contains a dispersion of the dyestutf and advantageously a dispersing agent, at a temperature in the vicinity of 100 C., if desired, with the addition of swelling agent, or at a temperature above 100 C. under superatmospheric pressure. As no dyestuffs for producing orange-red dyeings on polyester fibers of good fastness to light and sublimation have hitherto been known, the dyestuifs of this invention constitute a valuable addition to the art.

The following examples illustrate the invention, the parts being by weight:

Example 1 2.55 parts of S-amino-l:4-dihydroxyanthraquinone are suspended in 40 parts of dry chlorobenzene and, after the addition of 1.8 parts of benzoyl chloride, the mixture is ICC boiled under reflux for 2 hours, allowed to cool and cooled to 5 C., filtered with suction, and the filter residue is washed with chlorobenzene and alcohol and dried. The dyestufl, which is obtained in good yield, crystallises from chlorobenzene in handsome orange-red crystals, which dissolvewith a red coloration in concentrated sulfuric acid.

In a state of fine dispersion the dyestuff dyes polyester fibers by the high temperature method or the method using a swelling agent, strong pure orange tints of excellent fastness to light and sublimation.

The S-amino-l:4-dihydroxyanthraquinone used in this example can be obtained as described in Journal fiir praktische Chemie (2) vol. 130, pages 92101 (1931) by reacting 5-chloro-l:4-dimethoxyanthraquinone with para-toluene sulfonamide followed by demethylation and the splitting ofi" of the para-toluene sulfonic acid group.

Example 2 25.5 parts of S-amino-quinizariu and 22 parts of 2- chlorobenzoyl chloride are boiled under reflux in 440 parts ofdry chlorobenzene for 3 hours under reflux. After being cooled, the mixture is stirred for /2 hour at 0-5 C., then filtered with suction, and the filter residue is washed with chlorobenzene, alcohol and petroleum ether and dried in vacuo at 65-70 C. The dyestulf, which is obtained in very good yield in the form of a red powder,

after being brought into fine dispersion, dyes polyester fibers, for example, by the high temperature method, pure orange tints having excellent properties of fastness.

Example 3 Example 4 25.5 parts of S-amino-quinizarin and 22 parts of 4-methoxy-benzoylchloride are boiled under reflux in 420 parts of dry chlorobenzene for 3 hours. After being cooled, the mixture is stirred for /2 hour at 0-5" G, filtered with suction, and the filter residue is washed with chlorobenzene, alcohol and petroleum ether and dried in vacuo at -70 C. The dyestulf, which is precipitated in the form of red crystals, after being brought into fine dispersion, dyes polyester fibers, for example, by the high temperature process, fast pure orange tints.

Example 5 25.5 parts of S-amino-quinizarin and 22 parts of 4- chlorobenzoyl chloride are boiled under reflux in 460 parts of dry chlorobenzene for 3 hours. After cooling the mixture, the red crystals of the dyestuff are filtered off with suction, Washed with chlorobenzene, alcohol and petroleum ether and dried in vacuo at 65-70 C. After being brought into fine dispersion, the dyestuif dyes polyester fibers, for example, by the high temperature method, very fast light yellow-red tints.

Example 6 25.5 parts of S-amino-quinizarin and 22' parts of phen a 4 oXy-acetylchloride are boiled under reflux in 380 parts of 4. 1,4-dihydroxy-5-acylaminoanthraquinone of the fordry chlorobenzene for 3 hours. After cooling the mixture mula it is stirred for /2 hour at 5 C., and the dystuft", which 0 OH precipitates in the form of a red crystalline powder, is 1| 1 filtered off with suction, washed with chlorobenzene, alco- 5 hol and petroleum ether and dried in vacuo at 6570 C. After being brought into fine dispersion, the dyestufi dyes polyester fibers brilliant orange tints. I

RCOHN O OH Example 7 10 18.4 parts of nicotinic acid are suspended in 400 parts in which is methylphenyl. of dry chlorobenzene and, after the addition of 21 parts 5. 1,4-d1hydroXy-5-acy1am1noanthraqu1nones of the forof thionyl chloride and a small amount of pyridine, the mula whole is slowly heated to 110 C., while stirring, then 0 OH stirred for 1 /2 hours at 110-120 C., cooled to 50 C., and H dry air is blown through the mixture for /2 hour. 25.5

parts of S-arnino-quinizarin are then added and the whole is slowly heated to the boil, then boiled under reflux for 3 hours, allowed to cool, filtered with suction at 0-5 C.,

and the filter residue is Washed with chlorobenzene, alco- RCOHN '0 OH hol and petroleum ether and dried in vacuo at 60 C.

The dyestuif is obtained in the form of red crystals which, in which R Stands for pyridyL after being brought into fine dispersion, dye polyester 6 The d estufi of the formula fibers, for example, by the high temperature method, pure y orange tints having good properties of fastness. (1? (DH Example 8 1 gram of the dyestufi obtained as described in the first paragraph of Example 1 is pasted with 1.5 grams of sulfite celluloe waste liquor or dinaphthyl-methane disul- I] fonic acid or a fatty alcohol-ethylene hydroxide condensal IH 0 0H tion product, and the mixture is diluted to 4000 cc. with L water with the addition of a further 1 cc. per liter of acetic acid of 40% strength and 1 gram per liter of a fatty alcohol-ethylene oxide condensation products. 100 35 7, Th d estufi f h f l grams of a yarn of polyester fibers are dyed for /2 to 1 hour at 115-132 C. in the dyebath so prepared, and a i deep orange dyeing of very good fastness to light is obtained.

What is claimed is: 49

1. 1,4-dihydroxy-5-acy1aminoanthraquinone of the for- [l mula onto-G001: o H

8. The dyestufr of the formula 0 OH ll RCOHN OH 50 in which R is an aromatic radical selected from the 1 1 group consisting of phenyl, pyridyl, hydroxyphenyl, lower CONE O OH alkoxyphenyl, lower alkylphenyl, trifiuorrnethylphenyl, halophenyl and phenoxyacetyl.

2. 1,4-dihydroxy-5-acylaminoanthraquinone of the formula I 9. The dyestufi of the formula 0 OH I O OH II ll 1 I I l I RCOHN O OH 7 @ocmoomr 0 on in which R is hydroxy phenyl.

3. 1,4-dihydroxy-5-acylarninoanthraquinone of the formula 10. The dyestufi of the formula OH [I l m I E R0 OHI I O H C ONE OH in which R- is methoxyphenyl.

6 11. 1,4-dihydroxy-5-acylaminoanthraquinone of the for- References Cited in the file of this patent mula O OH UNITED STATES PATENTS II I 2,691,027 Grossman Oct. 5, 1954 5 2,819,288 Grossman Jan. 7, 1958 OTHER REFERENCES RCOHN OH Waldmann: J. Prakt. Chem, vol. 130, pages 92-102 in which R- is trifluormethylphenyl 10 23 Ch h 12. 1,4*dihydroxy-S-acylaminoanthraquinofie of the for- 3 fig g 1212; ig:. I I H, pages mula 0 011 American Dyestufi Reporter, July 5, 1954, pages 426- II I 437.

15 Schroeder et aL: Textile Research Journal, vol. XXVII,

No. 4, April 1957, pages 2758285.

ROOHN on in which R- is halophen-yl. 20 

1. 1,4-DIHYDROXY-5-ACYLAMINOANTHRAQUINONE OF THE FORMULA 